EP0699190B1 - Preparation of 3-mercapto-5-amino-1h-1,2,4-triazole - Google Patents
Preparation of 3-mercapto-5-amino-1h-1,2,4-triazole Download PDFInfo
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- EP0699190B1 EP0699190B1 EP94918123A EP94918123A EP0699190B1 EP 0699190 B1 EP0699190 B1 EP 0699190B1 EP 94918123 A EP94918123 A EP 94918123A EP 94918123 A EP94918123 A EP 94918123A EP 0699190 B1 EP0699190 B1 EP 0699190B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
Definitions
- the invention relates to processes for the preparation of 3-mercapto-5-amino-(1H)-1,2,4-triazole or a salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the process of the invention involves the step of contacting a metal salt of the anion of formula I, wherein R-S is any suitable leaving group, with hydrazine or hydrazine hydrate for a sufficient time to form a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- 3-mercapto-5-amino-(1H)-1,2,4-triazole has utility as an intermediate in organic synthesis.
- European Patent Application No. 142,152 describes the preparation of organic herbicidal compounds from 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- U.S. Patent No. 5,068,347 describes the rearrangement of 2,5-diamino-1,3,4-thiadiazole at 80°C in aqueous NaOH.
- British Patent No. 1,232,838 describes the condensation of carbon disulfide and a salt of aminoguanidine to produce guanidinodithiocarbarmic acid which was then treated with boiling alkali to produce a triazole.
- U.S. Patent No. 4,543,309 describes the cyclization of N-guanidinothiourea hydrochloride in refluxing aqueous caustic followed by acidification. Godfrey and Kurzer, J. Chem. Soc. (1960) 3437, treated [amino(amidino)]-thioureas with acid which produced a triazole and amine and ketone by-products.
- 6334d 2-cyanoiminothiazolidinone is prepared by the reaction of a methyl N-cyanodithioiminocarbonate anion with a 2-haloethylamine or ethylenimine.
- metal salts includes metal salts having monovalent, bivalent and fractions of polyvalent metals sufficient to balance the anionic charge in the salt. Mixed metal salts are also contemplated.
- metal hydroxide includes hydroxides of monovalent, bivalent and polyvalent metals.
- Group 1 or Group 2 metals includes all metals from Groups 1 and 2 of the Periodic Table.
- methanolic solvent system includes methanol, aqueous methanol, or any mixture of solvents including methanol.
- a methanolic solvent system may include methanol and one or more other solvents, such as water, ethanol or acetone.
- the invention provides a novel process for preparing 3-mercapto-5-amino-(1H)-1,2,4-triazole or a salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the invention can also provide a process for preparing 3-mercapto-5-amino-(1H)-1,2,4-triazole or a salt of 3-mercapto-5-amino(1H)-1,2,4-triazole which can be rapid and efficient and which can provide good product yield and purity.
- the invention provides a process comprising the step of (c) contacting a Group 1 or 2 metal salt of the anion of formula I wherein R-S is any suitable leaving group, with hydrazine or hydrazine hydrate for a sufficient time to form a Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the invention provides a process, prior to step (c), comprising the steps of:
- the invention is directed to a process for the preparation of a salt of 3-mercapto-5-amino-(lH)-1,2,4-triazole which involves the step of contacting a Group 1 or 2 metal salt of the anion of formula I, wherein R-S is any suitable leaving group, with hydrazine or hydrazine hydrate for a sufficient time to form a Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole, preferably by acidification.
- this process uses a Group 1 metal (A) and may be depicted as follows:
- the Group 1 or 2 metal salt of the anion of formula I may be prepared by a process which involves the steps of:
- this process uses a Group 1 metal (A) and a compound containing an R-group (R-X). This process may be depicted as follows:
- a combination of the above two processes involves the steps of:
- this process uses a Group 1 metal (A) and a compound containing an R-group (R-X). This process may be depicted as follows:
- a Group 1 or 2 metal salt of 3-mercapto-5-(1H)-1,2,4-triazole can be prepared in high yield and high purity by preparing a metal salt of N-cyanodithioiminocarbonate, which is then used to prepare a metal salt of S-substituted N-cyanodithioiminocarbonate, which is then reacted with hydrazine or hydrazine hydrate to produce a Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- the metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may then be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole by means known to those skilled in the art, such as acidification.
- N-cyanodithioiminocarbonates have been prepared by various methods, such as contacting cyanamide and carbon disulfide, in a solvent of aqueous ethanol, water or absolute ethanol, with a solution of a metal hydroxide.
- a metal salt of N-cyanodithioiminocarbonate in which solid cyanamide and solid potassium hydroxide react in ethanol followed by isolation of the precipitated solid product.
- the preparation of a Group 1 or 2 metal salt of N-cyanodithioiminocarbonate may involve contacting cyanamide, carbon disulfide, and a Group 1 or 2 metal hydroxide, under conditions sufficient to produce a Group 1 or 2 metal salt of the anion of formula II
- the preparation of a Group 1 or 2 metal salt of N -cyanodithioiminocarbonate involves contacting cyanamide, carbon disulfide, and Group 1 or 2 metal hydroxide in any suitable solvent. More preferably the solvent is methanol, aqueous methanol, water, ethanol, aqueous ethanol, acetone or mixtures of these. Most preferably, the cyanamide, carbon disulfide, and Group 1 or 2 metal are contacted in a methanolic solvent system.
- a solution of aqueous cyanamide and carbon disulfide is contacted with a Group 1 (alkaline) metal hydroxide, in a methanolic solvent system, to produce a bis-alkaline metal salt of N -cyanodithioiminocarbonate.
- a Group 1 (alkaline) metal hydroxide in a methanolic solvent system, to produce a bis-alkaline metal salt of N -cyanodithioiminocarbonate.
- the preferred methanolic solvent system may be methanol, aqueous methanol, or any mixture of solvents including methanol.
- a methanolic solvent system may include methanol and one or more other solvents, such as water, ethanol or acetone.
- the amount of methanol in the reaction mixture is at least 25% of the total volume, excluding the carbon disulfide volume. More preferably, the amount of methanol in the reaction mixture is about 90% of the total volume, excluding the carbon disulfide volume. Most preferably, the amount of methanol in the reaction mixture is about 50% of the total volume, excluding the carbon disulfide volume. Lower percentages of methanol may also be used.
- the reaction mixture containing a lower percentage of methanol may have some green or orange discoloration, which is not necessarily undesirable.
- the reaction can be completed in about 2 hours. This reaction produces a yellow solution with a neutral to alkaline pH of generally 7-8.5.
- a methanolic solvent system in the production of metal salts of N -cyanodithioiminocarbonate can be a significant improvement over other solvent systems.
- the reaction for the production of a bis-alkaline metal salt of N -cyanodithioiminocarbonate may be performed in ethanol.
- a reaction in a methanolic solvent system possesses several advantages over a reaction in ethanol or other known solvents including, inter alia, a lower cost, a greater ease of separation from water for reuse, and a higher purity product.
- N -cyanodithioiminocarbonates can be used in further reactions, for example, to produce a mono-alkaline metal salt of mono-S-substituted N -cyanodithio-iminocarbonate.
- the metal salts of N -cyanodithioiminocarbonates may be kept in the methanolic solvent system or they may be isolated prior to further reactions.
- a mono-S-substituted N -cyanodithioiminocarbonate has been prepared by a method reported by Timmons and Wittenbrook, J. Org. Chem., 32:1566 (1967).
- potassium methyl N -cyanodithioiminocarbonate is prepared by adding a solution of methyl iodide in acetone at about 0°C to an aqueous acetone solution of dipotassium N-cyanodithioiminocarbonate.
- the reaction mixture is concentrated, and the product is freed from the potassium iodide (KI) by-product by dissolving the product in acetone and removing the KI by filtration.
- the acetone solution is concentrated and the solid product is washed with ether.
- the preparation of a metal salt of mono-S-substituted N -cyanodithioiminocarbonate may involve contacting a Group 1 or 2 metal salt of the anion of formula II with at least one compound containing an R-group under conditions sufficient to form a Group 1 or 2 metal salt of the anion of formula I wherein the R-S group is any suitable leaving group.
- the compound or compounds containing an R-group preferably provide at least one molar equivalent of the group R and less than two molar equivalents of the group R.
- the preparation of a Group 1 or 2 metal salt of mono-S-substituted N -cyanodithioiminocarbonate involves contacting a Group 1 or 2 metal salt of the anion of formula II and at least one compound containing an R-group in any suitable solvent. More preferably the solvent is methanol, aqueous methanol, water, ethanol, aqueous ethanol, acetone or mixtures of these. Most preferably, the Group 1 or 2 metal salt of the anion of formula II and at least one compound containing an R-group are contacted in a methanolic solvent system.
- the preferred preparation of a metal salt of mono-S-substituted N -cyanodithioiminocarbonate in a methanolic solvent system can be more rapid and efficient than the prior art processes.
- the methanolic solvent system may be methanol, aqueous methanol, or any mixture of solvents including methanol, as described above.
- Preferred methanolic solvent systems for the preparation of metal salts of mono-S-substituted N -cyanodithioimino-carbonates are the same as those described for the preparation of metal salts of N -cyanodithioiminocarbonates.
- R is preferably selected from substituted or unsubstituted, branched or unbranched C 1 -C 20 alkyl, C 2 -C 20 alkenyl or C 2 -C 20 alkynyl groups; monocyclic or polycyclic, fused or nonfused, carbocyclic or heterocyclic, substituted or unsubstituted aryl groups; hydrogen; and non-aryl, monocyclic or polycyclic, fused or nonfused, substituted or unsubstituted heterocyclic groups; or R-S is preferably selected from thiosulfonates; sulfonates, thioesters and thiocarbamates.
- R is selected from substituted or unsubstituted, branched or unbranched C 1 -C 6 alkyl groups. More preferably, R is methyl, ethyl, propyl, or isopropyl, and most preferably, R is methyl.
- the compound containing an R-group is a group R-X, wherein X is chloride, iodide, bromide or a group R-X-R, wherein X is a divalent group such as sulfate (SO 4 2- ).
- the compound containing an R-group may be selected from methylating agents CH 3 X and (CH 3 ) 2 X, such as methyl chloride, methyl iodide, or dimethyl sulfate.
- the compound containing an R-group is methyl chloride or dimethyl sulfate.
- an aqueous methanolic solution of a bis-alkaline metal salt of N -cyanodithioiminocarbonate such as disodium N -cyanodithio-iminocarbonate or dipotassium N -cyanodithioiminocarbonate
- a compound containing an R-group such as methyl chloride
- a mono-S-substituted N -cyanodithioiminocarbonate such as sodium methyl N -cyanodithio-iminocarbonate or potassium methyl N -cyanodithioiminocarbonate
- the reaction mixture can be concentrated to recover the methanol and isolate the reaction product.
- the salt is a sodium salt
- the sodium methyl N -cyano-dithioiminocarbonate product can be obtained as a viscous yellow mixture which can contain NaCl.
- the salt is a potassium salt
- the potassium methyl N -cyanodithioiminocarbonate product can be obtained as a yellow-white solid.
- the mono-S-substituted N -cyanodithioiminocarbonate product can be purified with at least one solvent, such as acetone and/or dichloromethane, prior to further reactions.
- a purification step may be performed to render the mono-S-substituted N-cyanodithio-iminocarbonate product essentially, or totally, free of by-products.
- the solid product may be freed from by-products, such as NaCl or KCl, by dissolving the product in a suitable solvent, such as acetone, and filtering.
- a suitable solvent such as acetone
- the solvent solution can then be concentrated to recover the solvent and, if concentrated, the resulting solid can be purified by suspending in a suitable solvent, such as dichloromethane, for a suitable time, such as 30 minutes, with agitation.
- the resultant slurry can then be filtered and the solid can be dried.
- Any disubstituted ester, such as the dimethyl ester, of N -cyanodithioimino-carbonate which may have formed during the reaction can be isolated from the filtrate.
- dichloromethane for the purification is an improvement over the use of diethyl ether because, unlike diethyl ether, dichloromethane is not flammable and does not form peroxides.
- the product may then be dried either in air for about twelve hours or under vacuum at about 50°C for about two hours.
- metal salts of S-substituted N -cyanodithioiminocarbonate which are preferably essentially free of contaminants and by-products, may be further reacted with hydrazine or hydrazine hydrate to produce a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- a preferred embodiment of the invention is a process comprising the step of contacting a Group 1 or 2 metal salt of the anion of formula I, wherein R-S is any suitable leaving group, with hydrazine or hydrazine hydrate for a sufficient time to form a Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- a further preferred embodiment of the invention is a process comprising the steps of:
- the group R In each of the processes for the preparation of metal salts of 3-mercapto-5-amino-(1H)-1,2,4-triazole, the group R, and the preferred embodiments of the group R, are the same as those described previously for the preparation of metal salts of mono-S-substituted N -cyanodithioiminocarbonates.
- R is methyl, ethyl, propyl, or isopropyl, and most preferably, R is methyl.
- the reaction to form a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole generally can be conducted at elevated temperatures in the range of 25°C to 100°C, although the reaction is not limited to this range. In a preferred embodiment, the reaction temperature is in the range of about 50°C to 60°C.
- a salt of mono-S-substituted N -cyanodithioiminocarbonate such as potassium methyl N -cyanodithioiminocarbonate or sodium methyl N -cyanodithio-iminocarbonate
- a salt of mono-S-substituted N -cyanodithioiminocarbonate such as potassium methyl N -cyanodithioiminocarbonate or sodium methyl N -cyanodithio-iminocarbonate
- Molarities of the salt are preferably in the range of 0.5 M to 4 M, and molarities in the range of 2 M to 4 M are more preferred.
- the reaction is exothermic and the reaction temperature is preferably maintained at about 50°C by controlling the rate of addition until all of the hydrazine or hydrazine hydrate is added.
- the reaction mixture is preferably kept at about 50°C for preferably 1.5 hours or until completion of the reaction, after which the mixture is cooled.
- a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be used to produce 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole by any means known to those skilled in the art.
- a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole by acidification.
- the acidification is performed by adding a sufficient amount of acid to the solution of a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole until the solution reaches a pH of about 4 to less than about 7. More preferably, a sufficient amount of an acid, such as hydrochloric acid, is added to the solution of a metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole until the solution reaches a pH of about 6.
- the solid 3-mercapto-5-amino-(lH)-1,2,4-triazole product can be washed with water or acetone, isolated by filtration, and dried.
- the yield of the 3-mercapto-5-amino-(1H)-1,2,4-triazole is preferably in the range of 75 to 100% and the product purity is preferably in excess of 94%.
- Cyanamide (40.5 g of 50% aqueous solution, 482 mmol, 1.0 equiv), 95% ethanol (96 mL), and carbon disulfide (36.6 g, 481 mmol, 1.0 equiv) were charged into a 1-L, three-necked, round-bottomed flask fitted with a thermometer, mechanical stirring paddle, addition funnel and nitrogen valve. The vessel was then purged with nitrogen for 10 minutes. The mixture was agitated and cooled to 5°C. A solution of base was prepared separately. Sodium hydroxide (38.6 g, 965 mmol, 2.0 equiv) was dissolved in 550 mL 95% ethanol over 1/2 h and the solution was cooled to room temperature.
- the addition funnel was charged with this solution.
- the solution of base was added to the cooled cyanamide mixture over 25 minutes while maintaining a temperature of 9°C.
- the yellow product mixture was stirred for 1 hour, and then the insoluble material was removed by filtration.
- This solution of disodium N -cyanodithio-iminocarbonate was used directly in a further reaction to produce sodium methyl N -cyanodithioiminocarbonate.
- Cyanamide (10.2 g of a 50% aqueous solution; 120.5 mmol, 1.0 equiv), 95% ethanol (60 mL), and carbon disulfide (9.24 g, 121.4 mmol, 1.01 equiv) were charged into a 100-mL, three-necked, round-bottomed flask fitted with a thermometer, nitrogen valve, an addition funnel (non-equalizing) and a stirring bar. The addition funnel was charged with sodium hydroxide (9.64 g, 241 mmol, 2.0 equiv) dissolved in 17 mL water. The cyanamide mixture was cooled to 1°C and the base solution was added dropwise over 34 minutes.
- the final temperature was 10°C and the temperature was allowed to rise to 15°C over 1 hour.
- the mixture was concentrated in vacuo, and the residual water was chased with 95% ethanol (2 x 50 mL).
- the yellow-white solid was suspended in ethanol, stirred for 10 minutes and filtered to yield 5.4 g (27%) of the disodium N -cyanodithioiminocarbonate as a white powder.
- the filtrate was concentrated to yield 16 g of slightly wet product.
- disodium N -cyanodithioiminocarbonate can be prepared in other solvents such as aqueous ethanol (25 to 60% water, preferably 50% water) or aqueous methanol (5 to 75% water, preferably 50% water) and at temperatures between 0 and 30°C.
- aqueous ethanol 25 to 60% water, preferably 50% water
- aqueous methanol 5 to 75% water, preferably 50% water
- Cyanamide (15.16 g of a 50% aqueous solution, 180 mmol, 1.0 equiv), methanol (40 mL), and carbon disulfide (13.7 g, 180 mmol, 1.0 equiv) were charged into a 100-mL, three-necked, round-bottomed flask equipped with a stirring bar, thermometer, and addition funnel. The system was sealed and potassium hydroxide (14.0 M, 25,7 mL, 360 mmol, 2.0 equiv) was added over 18 minutes while the reaction temperature was maintained at under 20°C. The mixture was stirred for 2 h and the resulting yellow slurry was tested for residual cyanamide, and its pH was determined.
- This slurry could be used as is in a further reaction to produce either 3-mercapto-5-amino-(1H)-1,2,4-triazole or dimethyl N -cyanodithioiminocarbonate assuming a 95% conversion to the S-methyl adduct.
- the compound can be isolated and identified by methods well known in the art.
- Example 6 was repeated using a methylating agent of dimethyl sulfate in place of methyl iodide, with the exception that the product sodium methyl N -cyanodithioiminocarbonate (57 g, as a yellow slurry) was converted to dimethyl N -cyanodithioiminocarbonate in a further reaction with a second equivalent of methyl iodide.
- the slurry was diluted with acetone (1 L), filtered to remove sodium methyl sulfate, and concentrated to a volume of 150 mL.
- This slurry could be used as is in a further reaction to produce either 3-mercapto-5-amino-(1H)-1,2,4-triazole or dimethyl N -cyanodithioiminocarbonate, assuming a 95% conversion to the S-methyl adduct.
- the compound can be isolated and identified by using methods known in the art.
- Example 8 was repeated using a reaction temperature of 5°C, with the exception that the addition of dimethyl sulfate required 50 minutes.
- the slurry was used as is in a further reaction to produce dimethyl N -cyanodithioiminocarbonate.
- the slurry could also be used to produce a high yield of 3-mercapto-5-amino-(1H)-1,2,4-triazole, assuming a 95% conversion to the S-methyl adduct.
- the compound can be isolated and identified by methods known in the art.
- sodium methyl N -cyanodithioiminocarbonate can be prepared in solvents such as aqueous ethanol (5 to 75% water, preferably 50% water) and at temperatures between 0 and 50°C.
- solvents such as aqueous ethanol (5 to 75% water, preferably 50% water) and at temperatures between 0 and 50°C.
- methylating agents such as dimethyl sulfate or methyl chloride, could be used in place of methyl iodide.
- Dipotassium N -cyanodithioiminocarbonate (348.2 g, 1.794 mol, 1.0 equiv), water (1.575 L), and acetone (1.450 L) were charged into a 5-L, three-necked, round-bottomed flask equipped with a mechanical stirrer, thermometer, a fritted glass inlet tube and an exit tube.
- the solution was cooled to 3°C and methyl chloride (102.8 g, 2.036 mol, 1.13 equiv) was added over 70 minutes while the temperature was maintained at less than 7°C.
- reaction mixture was stirred overnight and then concentrated to give a wet yellow-white paste which was suspended in acetone (1.25 L; 4 mL/g of product) and stirred for 5 minutes.
- the mixture was filtered to yield 124 g (93%) of white potassium chloride.
- a sample of this solid was dissolved in water to give a clear colorless solution indicating that all the starting dipotassium salt had been consumed.
- the filtrate was concentrated in vacuo at 50°C to a yellow-white solid, which was suspended in methylene chloride (900 mL; 3 mL/g of product; to remove dimethyl N -cyanodithioiminocarbonate side product) and was stirred for about 30 minutes.
- the filtrate was concentrated at 50°C to a yellow-white solid, which was suspended in methylene chloride (200 mL; 3 mL/g of product; to remove dimethyl N -cyanodithioiminocarbonate side product) and was stirred for about 30 minutes.
- the solid was collected by filtration, washed with methylene chloride (10 mL) and dried to yield 26.0 g (85%) of a faint pink crystalline solid which is potassium methyl N-cyanodithio-iminocarbonate.
- the methylene chloride filtrate was concentrated to yield 1.7 g (9%) of dimethyl N -cyanodithioiminocarbonate.
- Portion B was stored overnight and concentrated to a yellow-white paste.
- the water was chased with 95% ethanol (50 mL), and the paste was suspended in acetone (320 mL) and stirred for 0.5 h.
- the mixture was filtered to yield wet potassium chloride and the yellow filtrate was dried (Na 2 SO 4 ), filtered and concentrated.
- the yield of dry product was 73.3 g (86%) as a granular yellow solid. This treatment of the product indicated that there was little decomposition of the potassium methyl adduct upon storage in the reaction mixture for about 12 hours.
- Portion C was treated with hydrazine as described in Example 18.
- the potassium chloride was washed with acetone (100 mL) and filtered.
- the methylene chloride filtrate was concentrated and the yellow-white paste was dissolved in acetone (375 mL) and filtered to remove a small amount of potassium chloride.
- the desired product 3-mercapto-5-amino-(1H)-1,2,4-triazole can be prepared from a mono-S-substituted N-cyanodithioiminocarbonate such as sodium methyl N-cyanodithioiminocarbonate or potassium methyl N-cyanodithio-iminocarbonate prepared according to any of the methods listed in Examples 6 through 14 above.
- a solution of potassium methyl N -cyanodithioiminocarbonate was prepared according to Example 13, using 1.25 moles of cyanamide, and approximately the same reaction times and temperatures.
- the reaction mixture containing the mono-methyl adduct was concentrated at 50°C at aspirator vacuum to remove the ethanol.
- the residue was diluted with water (300 mL) to give an aqueous solution of potassium methyl N -cyanodithioiminocarbonate of 25 wt%.
- the solution was treated with hydrazine hydrate (about 74 g of a 54.4 wt% aqueous solution, 1.255 mol, 1.0 equiv) in the same manner as given in Example 15, except that the addition required 45 minutes.
- the 3-mercapto-5-amino-(1H)-1,2,4-triazole product was precipitated by acidification of the reaction mixture to pH 5 and was isolated by filtration.
- the yield of 3-mercapto-5-amino-(1H)-1,2,4-triazole was 96 g (66%) with a purity of 96.5%.
- Example 16 The experiment of Example 16 was repeated except that 1.496 moles of cyanamide were used and the percentage concentration of potassium methyl N -cyanodithioiminocarbonate after removal of the ethanol and dilution with water was 30 wt%.
- the product triazole was obtained in like manner to Example 16 except that the pH of the reaction mixture was adjusted to 6.
- the yield of triazole was 118 g (68%) with a purity of 97.3%.
- Example 13 which was a 25 wt% aqueous solution of potassium methyl N -cyanodithioiminocarbonate after dilution with water, was warmed to 45°C and hydrazine (54.4 wt% in water, 29.44 g, 0.500 mol, approx. 1 equiv) was added over 33 minutes, and the resulting solution was stirred at 45°C for 2.25 hours.
- the solution was cooled to 25°C and concentrated HCl was added until a pH of 6 was obtained (about 36 mL of conc. HCl). The mixture was stirred for 1 hour and filtered. The filter cake was washed with water (100 mL) and acetone (100 mL) and dried in vacuo to yield 38 g (65.5%) of the triazole of 96.7% purity.
- a solution of potassium methyl N -cyanodithioiminocarbonate was prepared according to Example 16, using 1.499 moles of cyanamide, and about the same time and temperatures except that the solution of dipotassium N -cyanodithio-iminocarbonate was kept overnight.
- the reaction mixture was concentrated to give a percent concentration of 30 wt% of the mono-methyl adduct in water. This aqueous solution was divided into four portions and each portion was treated with hydrazine hydrate according to the method of Example 15 with the parameters listed in the Table, except that the four solutions of the potassium salt of the triazole were stored overnight. Portion Equiv.
- the solution was acidified to pH 4.6 with concentrated HCl and the solid was collected by suction, washed with water, acetone and dried.
- the yield of the desired triazole was 5.3 g (77%) with a purity of 98.5%. This Example demonstrates that the purity of the triazole is directly dependent on the purity and the types of washes used to purify the potassium methyl salt.
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Abstract
Description
(c) contacting a Group 1 or 2 metal salt of the anion of formula I wherein R-S is any suitable leaving group, with hydrazine or hydrazine hydrate for a sufficient time to form a Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole. The Group 1 or 2 metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole may be converted to 3-mercapto-5-amino-(1H)-1,2,4-triazole.
Portion | Equiv. H2NNH2 | pH | Amount | Yield | Purity (color) |
1 | 1.25 | 6 | 31 | 72 | 96.4 |
2 | 1.50 | 6 | 30.7 | 71 | 96.6 |
3 | 1.75 | 5.8 | 29 | 67 | N/D (off-white) |
4 | 2.00 | 4.5 | 32 | 74 | N/D (grey) |
N/D = not determined |
Claims (12)
- The process according to claim 1 further comprising, prior to step (c), the steps of:(a) contacting cyanamide, carbon disulfide, and a Group 1 or 2 metal hydroxide under conditions sufficient to produce a Group 1 or 2 metal salt of the anion of formula II
- The process according to claim 1 or 2, wherein said Group 1 or 2 metal is potassium or sodium.
- The process according to claim 1 or 2, wherein R is selected fromsubstituted or unsubstituted, branched or unbranched C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkynyl groups;monocyclic or polycyclic, fused or nonfused, carbocyclic or heterocyclic, substituted or unsubstituted aryl groups;hydrogen; andnon-aryl, monocyclic or polycyclic, fused or nonfused, substituted or unsubstituted heterocyclic groups;
or R-S is selected fromthiosulfonates;sulfonates;thioesters; andthiocarbamates. - The process according to claim 4, wherein R is selected from substituted or unsubstituted, branched or unbranched C1-C6 alkyl groups.
- The process according to claim 1 or 2, wherein said metal salt of said anion of formula I and said hydrazine or hydrazine hydrate are contacted in a solvent, preferably water.
- The process according to claim 1 or 2, wherein said metal salt of said anion of formula I and said hydrazine or hydrazine hydrate are contacted at a temperature ranging from 50° to 60° C.
- The process according to claim 1 or 2, further comprising the step of converting said metal salt of 3-mercapto-5-amino-(1H)-1,2,4-triazole to 3-mercapto-5-amino-(1H)-1,2,4-triazole.
- The process according to claim 8, wherein said conversion is accomplished by acidification, preferably by adding an amount of acid sufficient to reach a product solution pH ranging from 4 to less than 7.
- The process according to claim 2, wherein said compound containing an R-group is methyl chloride, methyl iodide or dimethyl sulfate.
- The process according to claim 2, wherein step (a) is carried out in a methanolic solvent system, preferably methanol or aqueous methanol.
- The process according to claim 1 or 2, further comprising the step of purifying said salt of the anion of formula I with at least one solvent prior to step (c), preferably acetone or dichloromethane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SI9430168T SI0699190T1 (en) | 1993-05-18 | 1994-05-18 | Preparation of 3-mercapto-5-amino-1h-1,2,4-triazole |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6253293A | 1993-05-18 | 1993-05-18 | |
US62532 | 1993-05-18 | ||
PCT/US1994/005892 WO1994026724A2 (en) | 1993-05-18 | 1994-05-18 | Preparation of n-cyanodithioimino-carbonates and 3-mercapto-5-amino-1h-1,2,4-triazole |
Publications (2)
Publication Number | Publication Date |
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EP0699190A1 EP0699190A1 (en) | 1996-03-06 |
EP0699190B1 true EP0699190B1 (en) | 1998-08-26 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP94918123A Expired - Lifetime EP0699190B1 (en) | 1993-05-18 | 1994-05-18 | Preparation of 3-mercapto-5-amino-1h-1,2,4-triazole |
Country Status (19)
Country | Link |
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US (1) | US5610311A (en) |
EP (1) | EP0699190B1 (en) |
JP (1) | JPH09501402A (en) |
CN (1) | CN1127505A (en) |
AT (1) | ATE170178T1 (en) |
AU (1) | AU681410B2 (en) |
BR (1) | BR9407071A (en) |
CA (1) | CA2162906A1 (en) |
CZ (1) | CZ298595A3 (en) |
DE (1) | DE69412820T2 (en) |
DK (1) | DK0699190T3 (en) |
ES (1) | ES2122287T3 (en) |
FI (1) | FI955555A0 (en) |
NO (1) | NO954663L (en) |
NZ (1) | NZ267319A (en) |
SG (1) | SG44509A1 (en) |
SK (1) | SK142295A3 (en) |
WO (1) | WO1994026724A2 (en) |
ZA (1) | ZA943337B (en) |
Families Citing this family (3)
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WO2006096159A1 (en) * | 2005-03-04 | 2006-09-14 | Buckman Laboratories International, Inc. | Fungicidal compositions and methods using cyanodithiocarbimates |
EP3350172A1 (en) * | 2015-09-15 | 2018-07-25 | Bayer Cropscience LP | Procedure for the preparation of 2-cyanoimino-1,3-thiazolidine |
CN110911749B (en) * | 2019-12-03 | 2023-02-03 | 珠海市赛纬电子材料股份有限公司 | High-voltage lithium ion battery electrolyte, additive and preparation method of additive |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US2816136A (en) * | 1956-10-22 | 1957-12-10 | Buckman Labor Inc | Process for the production of alkali and alkaline-earth-metal salts of cyanodithioimidocarbonic acid |
GB1232838A (en) * | 1968-12-05 | 1971-05-19 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB737568A (en) * | 1952-06-11 | 1955-09-28 | Ilford Ltd | Improvements in or relating to cyclic nitrogen compounds |
NL103060C (en) * | 1956-10-10 | |||
US2881071A (en) * | 1957-07-12 | 1959-04-07 | Buckman Labor Inc | Processes for the control of slime-forming and other microorganisms and compositions for use therefor |
US3299129A (en) * | 1963-12-13 | 1967-01-17 | Monsanto Co | Cyanoimidodithiocarbonates |
DD113362A1 (en) * | 1974-02-07 | 1975-06-05 | ||
JPS58193541A (en) * | 1982-05-07 | 1983-11-11 | Konishiroku Photo Ind Co Ltd | Heat developable image recording material |
JPS6028969A (en) * | 1983-07-26 | 1985-02-14 | Fujimoto Seiyaku Kk | Production of 2-cyanoiminothiazolidine |
EP0142152B1 (en) * | 1983-11-14 | 1991-03-20 | The Dow Chemical Company | Novel substituted 1,2,4-triazolo- [1,5-a] pyrimidine-2-sulfonamides and compositions and methods of controlling undesired vegetation and suppressing the nitrification of ammonium nitrogen in soil |
DD256693A1 (en) * | 1985-09-27 | 1988-05-18 | Bitterfeld Chemie | PROCESS FOR PREPARING CYANIMIDODITHIOCHOKENOEENESTERS |
US5068347A (en) * | 1987-11-23 | 1991-11-26 | Dowelanco | Process for the preparation of 3-mercapto-5-amino-(1h)-1,2,4-triazole |
-
1994
- 1994-05-16 ZA ZA943337A patent/ZA943337B/en unknown
- 1994-05-18 CZ CZ952985A patent/CZ298595A3/en unknown
- 1994-05-18 WO PCT/US1994/005892 patent/WO1994026724A2/en not_active Application Discontinuation
- 1994-05-18 DE DE69412820T patent/DE69412820T2/en not_active Expired - Fee Related
- 1994-05-18 SK SK1422-95A patent/SK142295A3/en unknown
- 1994-05-18 ES ES94918123T patent/ES2122287T3/en not_active Expired - Lifetime
- 1994-05-18 SG SG1996001182A patent/SG44509A1/en unknown
- 1994-05-18 CA CA002162906A patent/CA2162906A1/en not_active Abandoned
- 1994-05-18 NZ NZ267319A patent/NZ267319A/en unknown
- 1994-05-18 DK DK94918123T patent/DK0699190T3/en active
- 1994-05-18 BR BR9407071A patent/BR9407071A/en not_active Application Discontinuation
- 1994-05-18 JP JP6525828A patent/JPH09501402A/en not_active Ceased
- 1994-05-18 EP EP94918123A patent/EP0699190B1/en not_active Expired - Lifetime
- 1994-05-18 CN CN94192813A patent/CN1127505A/en active Pending
- 1994-05-18 AU AU69580/94A patent/AU681410B2/en not_active Ceased
- 1994-05-18 AT AT94918123T patent/ATE170178T1/en active
-
1995
- 1995-04-18 US US08/425,221 patent/US5610311A/en not_active Expired - Fee Related
- 1995-11-17 NO NO954663A patent/NO954663L/en unknown
- 1995-11-17 FI FI955555A patent/FI955555A0/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2816136A (en) * | 1956-10-22 | 1957-12-10 | Buckman Labor Inc | Process for the production of alkali and alkaline-earth-metal salts of cyanodithioimidocarbonic acid |
GB1232838A (en) * | 1968-12-05 | 1971-05-19 |
Also Published As
Publication number | Publication date |
---|---|
DK0699190T3 (en) | 1998-11-09 |
SG44509A1 (en) | 1997-12-19 |
DE69412820T2 (en) | 1999-01-14 |
ATE170178T1 (en) | 1998-09-15 |
CA2162906A1 (en) | 1994-11-24 |
NO954663L (en) | 1995-11-20 |
CZ298595A3 (en) | 1996-04-17 |
NZ267319A (en) | 1997-12-19 |
ZA943337B (en) | 1995-01-27 |
US5610311A (en) | 1997-03-11 |
ES2122287T3 (en) | 1998-12-16 |
AU681410B2 (en) | 1997-08-28 |
JPH09501402A (en) | 1997-02-10 |
SK142295A3 (en) | 1996-09-04 |
EP0699190A1 (en) | 1996-03-06 |
CN1127505A (en) | 1996-07-24 |
WO1994026724A2 (en) | 1994-11-24 |
DE69412820D1 (en) | 1998-10-01 |
WO1994026724A3 (en) | 1995-01-19 |
FI955555A (en) | 1995-11-17 |
BR9407071A (en) | 1996-08-13 |
FI955555A0 (en) | 1995-11-17 |
AU6958094A (en) | 1994-12-12 |
NO954663D0 (en) | 1995-11-17 |
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